/ 


EXCHANGE 


I. 

The    Detection    of    Mannite    in     Alkaline 
Solutions  of  Copper  Sulphate 

Combustion  of  Mannite  by  Alkaline 

Solutions  of  Potassium  Permanganate  in  the 

Presence  of  Copper  Sulphate 


|L 

A  Determination  of  the  Volumes  of  Weight 

—Normal  Solutions  of  Cane  Sugar 

at  15°,  20°,  25°,  and  30° 


DISSERTATION 

SUBMITTED  TO  THE  BOARD  OF  UNIVERSITY  STUDIES  OF  THE 

JOHNS  HOPKINS  UNIVERSITY  IN  CONFORMITY  WITH 

THE  REQUIREMENTS  FOR  THE  DEGREE  OF 

DOCTOR    OF    PHILOSOPHY, 


BY 

HENRY  OTTO  EYSSELL, 

BALTIMORE, 

1912. 


GEO.  W.  KING  PRINTING  Co., 
BALTIMORE,  Mo. 


. 

The    Detection    of     Mannite    in     Alkaline 
Solutions  of  Copper  Sulphate 

Combustion  of  Mannite  by  Alkaline 

Solutions  of  Potassium  Permanganate  in  the 

Presence  of  Copper  Sulphate 


II. 

A  Determination  of  the  Volumes  of  Weight 

—Normal  Solutions  of  Cane  Sugar 

at  15°,  20°,  25°,  and  30° 


DISSERTATION 

SUBMITTED  TO  THE  BOARD  OF  UNIVERSITY  STUDIES  OF  THI 

JOHNS  HOPKINS  UNIVERSITY  IN  CONFORMITY  WITH 

THE  REQUIREMENTS  FOR  THE  DEGREE  OF 

DOCTOR    OF    PHILOSOPHY. 


r>v 

HENRY  OTTO  .]•  YSSKF.L 
BALTIMORE. 


GEO.  W.  KING  PRINTING  Co.. 
BALTIMORE,  MD. 


CONTENTS. 

Acknowledgment    5 

I.  Detection  of  Maimite. 

Introduction    7 

Method 7 

Strength  of  Solutions  Used 8 

Results  . 9 

Structure  of  Compound  Formed 15 

Conclusion    1(1 

Combustion  of  Ma  unite — 

Introduction    17 

Results 17 

Method 18 

Check  Experiments  19 

II.  Volume  Determinations. 

Introduction    20 

Apparatus    20 

Constant  Temperature  Bath 22 

Calculations    2:; 

Rotations  of  Solutions 24 

Results    24 

Summary  and  Conclusions 29 

Biography    .31 


253952 


ACKNOWLEDGMENT. 

The  author  wishes  to  express  his  sincere  gratitude  to  Presi- 
dent Remsen,  Professors  Morse,  Jones,  Acree,  Lovelace  and 
Whitehead  for  instruction  received  in  the  lecture  room  and  in 
the  laboratory. 

To  Professor  Morse,  the  writer  wishes  to  express  especial 
thanks  for  his  personal  direction  of  these  investigations  and 
also  to  Drs.  Frazer  and  Holland  for  many  valuable  sugges- 
tions. 


PART  1. 

Tin-    Detection   of   Mannite   in    All-aline   Solutions   of  Copper 

Sulphate. 

The  measurement  of  the  osmotic  pressure  of  solutions,  which 
has  been  in  progress  in  this  laboratory  for  the  last  ten  or 
twelve  years,  for  the  purpose  of  determining  whether  this  force 
obeys  the  laws  of  gas  pressure  or  not,  has  thus  far  been  con- 
fined mainly  to  solutions  of  cane  sugar  and  glucose.  As  soon 
as  practicable,  other  substances  will  be  dealt  with,  and  mannite 
will  probably  be  one  of  the  first. of  these. 

In  the  work  with  cane  sugar  and  glucose,  changes  in  the  con- 
centration of  their  solutions  can  be  detected  by  means  of  the 
polarimeter.  This  method  can  not  be  employed  in  the  case  of 
mannite,  which  made  it  desirable  to  work  out  another  for  this 
substance  just  as  delicate,  or  even  more  so,  than  the  one  based 
upon  the  rotatory  power  of  cane  sugar  and  glucose. 

When  the  cells  containing  the  solutions  whose  osmotic  pres- 
sure is  to  be  measured,  are  set  up,  they  are  immersed  in  a  vessel 
containing  an  0.01th  ion  X,  solution  of  copper  sulphate,  while 
the  cells  themselves  always  contain  a  quantity  of  an  0.01  ion  X. 
solution  of  potassium  ferrocyanide  besides  the  solutions  in 
question.  These  quantities  are  believed  to  be  osmotically 
equivalent,  and  they  are  used  in  this  manner  for  the 
purpose  of  repairing  ruptures  which  may  develop  in  the  mem- 
brane while  the  cells  are  giving  a  measurement. 

It  was  found  that  when  a  solution  of  mannite  is  made  alka- 
line with  potassium  hydroxide  and  there  is  then  added  to  it  a 
small  quantity  of  copper  sulphate,  <i  fine  blur  color  is  dcreloped 
without  precipitation  of  copper  hydroxide.  If  more  copper 
sulphate  is  added,  a  /trecipitate  of  copper  hi/dro.ri<]< 
and  if  still  wore  of  the  copper  sulphate  is  added,  the  fine 


8 

color  referred  to  eventually  disappears,  leaving  the  mannite  un- 
combined  witli  the  copper,  but  still  in  solution. 

At  temperatures  between  0°  and  60°,  all  solutions  are  made 
up  with  0.001  N.  thymol  water  to  prevent  the  growth  of  the 
mould  penicillium  glaucum,  which  it  seems,  thrives  upon  the 
nitrogen  of  the  ferrocyanogen  anion  of  the  membranes  and  de- 
stroys them.  It  was  possible  that  the  thymol  might  affect  this 
color  reaction,  or  give  a  similar  one  under  the  same  conditions, 
but  such  was  found  not  to  be  the  case.  When  solutions  of 
copper  sulphate  containing  thymol  in  quantities  sufficient  to 
make  them  0.001  N.  with  respect  to  the  latter  substance,  are 
treated  with  a  solution  of  potassium  hydroxide  and  filtered 
through  asbestos  the  filtrates  are  clear  and  colorless. 

This,  then,  seemed  to  be  a  practicable  method  for  detecting 
the  presence  of  mannite  in  solution  when  other  substances  which 
act  similarly  are  known  to  be  absent.  Several  other  poly-acid 
alcohols  (glycerol,  erythrite  and  arabite)  were  found  to  con- 
duct themselves  in  an  analogous  manner. 

The  solutions  of  copper  sulphate  and  of  mannite  used  in  the 
subsequent  work,  were  made  up  with  .001  N.  thymol  water, 
while  the  solution  of  potassium  hydroxide  was  made  up  with 
pure  water.  The  solutions  of  copper  sulphate  were  0.1  and  0.01 
volume  normal,  that  of  potassium  hydroxide  was  approximately 
0.5  N.,  each  cubic  centimeter  containing  .02805  grams.  The 
solution  of  mannite  contained  one  milligram  of  the  alcohol  per 
cubic  centimeter. 

Table  1  contains  the  quantities  of  mannite  and  the  maximum 
quantities  of  copper  sulphate,  which  in  100  cubic  centimeters 
of  solution,  were  found  to  give  a  blue  colored  filtrate  after  the 
addition  of  5  cubic  centimeters  of  the  potassium  hydroxide 
solution.  When  the  copper  sulphate  exceeded  the  quantities 
tabulated  by  one-tenth  of  a  milligram,  the  filtrates  became 
practically  colorless. 


TABLE  1. 

Maximum      iian- 

Manuite.  of  Topper  Sulphate. 

1  mg.  37      ing. 

2  mg.  88     mg. 

3  nig.  107.S  mg. 

4  mg.  144.0  mg. 

5  mg.  180.0  mg. 
•  I  ing.  1^7.1   mg. 

7  nig.  •  198.3  ing. 

8  mg.  236      mg. 
!>  mg.  24.~i.4  mg. 

10  nig.  261      mg. 

Table  :!  contains  The  results  which  were  obtained  when  an 
attempts  was  made  to  duplicate  those  given  in  Table  1.  The 
<-anse  for  whatever  discrepancies  there  are  between  the  results 
in  the  two  tables  was  found  to  be  due  to  the  fact  that  the 
asbestos  filter  absorbs  and  retains  some  of  the  coloring:  matter. 

TABLE  2. 

Ma  unite.  Maximum  Quantities 

of  Copper  Sulphate. 
1  mg.  36.3  mg. 

1  mg.  32.2  mg. 

2  mg.  88.0  mg. 

2  mg.  97.9  mg. 

3  mg.  121.4  mg. 

3  mg.  131.4  mg. 

4  mg.  144.0  mg. 

4  mg.  153.9  mg. 

5  mg.  179  9.  mg. 
5  mg.  177.7  nig. 
0  mg.  ir.vs  mg. 


Table  3  contains  ihe  Quantities  of  copper  sulphate  and  the 
minimum  quantities  of  mannite  which,  in  100  cubic  centimeters 
of  solution,  were  found  to  give  a  characteristically  colored  fil- 
trate after  adding  .">  cc.  <>f  the  alkali  solution. 

TABLE  3. 

Minimum  Quantity 
Sulphate.  of  Mauuite. 

10  nig.  0.3  mg. 

20  nig.  0.5  mg. 

30  mg.  O.G  mg. 

40  mg.  1.1   mir. 

•~<>  in-.  1.4  mg. 


10 

Table  4  contains  the  quantities  of  inannite  and  the  maximum 
quantities  of  copper  sulphate,  which  were  found  to  give  the  col- 
ored filtrate  in  200  cc.  of  solution  after  adding  5  cc.  of  the  alkali 
solution, 

TABLE  4. 

Maximum  Quantity 

Mannite.  •    of  Copper  Sulphate. 

1  mg.  34  mg. 

2  mg.  64  mg. 

3  mg.  92  mg. 

4  mg.  122  mg. 

5  mg.  154  mg. 

Table  5  contains  the  quantities  of  copper  sulphate  and  the 
minimum  quantities  of  mannite,  which  were  found  to  give  a 
colored  filtrate  in  200  cc.  of  solution,  after  making  alkaline 
with  5  cc.  of  the  potassium  hydroxide  solution . 

TABLE  5. 

Minimum  Quantity 
Copper  Sulphate.  of  Mannite. 

10  mg.  0.4  mg. 

20  mg.  0.7  nig. 

30  mg.  .                                  0.9  mg. 

40  mg.  1.3  mg. 

50  mg.  1.6  mg. 

Tables  f>  and  7  contain  the  results  obtained  in  100  cc.  of 
solution  when  the  ratio  of  mannite  to  copper  sulphate  was  kept 
constant.  The  mode  of  proceedure  here  and  in  the  following 
cases  was  the  same  as  stated  above. 

TABLE  6. 

Mannite.  Copper  Sulphate.  Filtrate. 

1  mg.  25  mg.  Colored. 

2  mg.  50  mg.  Colored. 

3  mg.  75  mg.  Colored. 

4  mg.  100  mg.  Colored. 

5  mg  125  mg.  Colored. 

6  mg.  100  mg.  Colored. 

7  mg.  175  mg.  Colored. 

8  mg.  200  mg.  Colored. 

9  mg.  225  mg.  Colored. 
10  mg.  250  mg.  Colorless. 


11 


The  last  filtrate  was  colored,  when  10  instead  of  5  cc.  of 
alkali  were  used. 


Ma  unite. 

1  ing. 

2  mg. 

3  mg. 

4  mg. 

5  mg. 

6  mg. 

7  mg. 

8  mg. 

9  mg. 
10  mg. 


TABLE  7. 

Copper  Sulphate. 

30  mg. 

60  mg. 

90  mg. 
120  mg. 
150  mg. 
180  mg. 
210  mg. 
240  mg. 
270  mg. 
300  mg. 

TABLE  8. 


Copper. 

Mamiite. 

Sulphate. 

Alkali. 

1  mg. 

60  mg. 

140.3  mg. 

1  mg. 

00  mg. 

500.0  mg. 

1  mg. 

70  mg. 

."00.0  mg. 

1  mg. 

SO  mg. 

500.0  mg. 

1  mg. 

90  mg. 

500.0  nig. 

Filtrate. 
Colored. 
Colored. 
Colored. 
Colored. 
Colored. 
Colored. 
Colored. 
Colorless. 
Colorless. 
Colorless. 


Filtrate. 
Colorless. 
Colorless. 
Colorless. 
Colorless. 
Colorless. 


The  filters  were  washed  with  10  cc.  of  the  alkali  solution. 
The  washings  were  all  colored. 

Asbestos  filters  were  used  throughout.  A  new  batch  of  asbes- 
tos was  prepared  at  this  st;ij>e  of  the  work.  It  was  considerably 
finer  than  that  previously  used,  and  with  it  colorless  filtrates 
were  obtained  with  ratios  which  had  given  colored  ones  before, 
ns  may  be  seen  from  the  results  given  in  table  9. 


TABLE  9. 


Mannir<>. 
1    m::. 
1  mp. 
1  mg. 
1   mir. 


Copper 
Sulphate 
i>.-  nig. 
1.5  ni.tr. 
25  nig. 
25  mg. 


Alkali. 

500  mg. 

750  mg. 
1000  mg. 
1250  mg. 


Filtrate. 
Colorless. 
Colorless. 
Colorless. 
Colorless. 


When  the  filters  were  washed  with  10  cc.  of  the  alkali  the 
washings  were  'not  colored.  They  were  deeply  colored,  how- 
ever, when  alkali  of  Fehling's  solution  strength  was  used. 
Blank  experiments  gave  colored  washings  with  the  strong  alk- 
ali, but  not  with  0.."  X. 


12 
TABLE  10. 

The  solutions  were  made  alkaline  with  5  cc.  of  the  potassium 
hydroxide  solution. 

Mannite.  Copper  Sulphate  Filtrate. 

1  mg.  25  mg.  Colorless. 

2  mg.  50  mg.  Colorless. 

3  mg.  75  mg.  Colored. 

4  mg.  100  mg.  Colored. 

5  nig.  125  mg.  Colored. 

6  mg.  150  mg.  Colored. 

The  filters  were  allowed  to  stand  for  about  15  minutes  with 
10  cc.  of  0.5  N.  alkali.  The  washings  were  all  colored. 

TABLE  11. 

Mannite.  Copper  Sulphate.  Filtrate. 

1  mg.  50  mg.  Colored. 

2  mg.  100  mg.  Colored. 

3  mg.  150  mg.  Colorless. 

4  mg.  200  mg.  Colorless. 

5  mg.  250  nig.  Colorless. 

6  mg.  300  mg.  Colorless. 

The  filters  were  allowed  to  stand  for  about  15  minutes  with 
10  cc.  of  the  0.5  N.  alkali.  The  washings  were  all  colored. 

TABLE  12. 

Mannite.  Copper  Sulphate.  Filtrate. 

1  mg.  75  mg.  Colorless. 

2  mg.  150  mg.  Colorless. 

3  mg.  225  mg.  Colorless. 

4  mg.  300  mg.  Colorless. 

5  mg.  375  mg.  Colorless. 

6  mg.  450  mg.  Colored. 

7  mg.  525  mg.  Colored. 

The  filters  were  allowed  to  stand  with  0.5  N.  alkali  as  stated. 
The  washings  were  all  colored,  excepting  those  obtained  from 
the  5  and  7  mg.  experiments.  Duplicate  experiments  gave  the 
same  results. 


13 
TABLE  13. 

The  solutions  were  made  alkaline  with  5  cc.  of  the  potassium 
hydroxide  solution. 


Maimite.  Copper   Sulphate.  Filtrate. 

1  jng.  100  mg.  Colorless. 

'2  ing.  200  mg.  Colorless. 

3  mg.  300  mg.  Colorless. 

4  mg.  400  mg.  Colored. 

5  mg.  500  mg.  Colored. 

6  mg.  600  mg.  Colored. 


The  filters  were  treated  with  0.5  X.  alkali  as  stated.  Where 
colorless  filtrates  were  obtained  the  washings  were  colored, 
and  vice  versa. 


TABLE  14. 

The  solutions  were  made  alkaline  with  5  cc.  of  the  potassium 
hvdroxide  solution. 


Mannite.  Copper  Sulphate.  Filtrate. 

1  mg.  10  mg.  Colored. 

2  mg.  20  mg.  Colored. 

3  ing.  30  mg.  Colored. 

4  mg.  40  mg.  Colored. 

5  mg.  50  mg.  Colored. 

6  mg.  60  mg.  Colored. 


The  filters  were  treated  as  in  previous  cases;  the  washings 
were  all  colored. 


The  results  tabulated  in  tables  6  to  14.  inclusive,  were  ob- 
tained in  100  cc.  of  solution.  Those  given  in  table  15  were  ob- 
tained in  100  cc.  of  .01  N.  copper  sulphate  solution. 


*  • 

14 

TABLE 

15. 

Mannite. 
1  mg. 

Copper 
Sulphate. 

123.92  mg. 

Alkali. 
5  cc. 
140.3  mg. 

Filtrate. 
Colorless. 

1  mg. 

123.92  mg. 

10  cc. 
2S0.5  mg. 

Colorless. 

1  mg. 

123.92  mg. 

15  cc. 
420.8  mg. 

Colorless. 

1  mg. 

123.92  mg. 

20  cc. 
tiGl.Omg. 

Colorless. 

1  nig. 

123.92  mg. 

25  cc. 
701.3  mg 

Colorless. 

1  mg. 

123.92  mg. 

30  cc. 
841  .5  mg. 

Colorless. 

1  mg. 

123.92  mg. 

40  cc. 
1122.0  mg. 

Slightly 
Colored. 

1  mg. 

3  23.92  mg. 

45  cc. 
1162.5  mg. 

Slightly 
Colored. 

1  mg. 

123.92  mg. 

50  cc. 
1402.5  mg. 

Slightly 
Colored. 

2  mg. 

123.92  mg. 

5  cc. 
140.3  mg. 

Colorless. 

2  mg. 

]  23.92  mg. 

30  cc. 
841.5  ing. 

Colored. 

2  mg. 

123.92  mg. 

50  cc. 
1420.5  mg. 

Colored. 

3  mg. 

]  23.92  mg. 

30  cc. 
841.5  mg. 

Colored. 

•r>  mg. 

123.92  mg. 

30  cc. 
841.5  mg. 

Deep 
Color. 

None. 

1  23.92  mg. 

30  cc. 
841.5  mg. 

Colorless. 

None. 

1  23.92  mg. 

50  cc. 
1  420.5  mg. 

Colorless. 

15 


The  color  of  the  filtered  solutions  is  probably  due  to  1he  for- 
mation of  one  of  the  following  compounds  : 


(1)    CH*OH 

CHOH 

CHOH+GCu(OH)2 

CHOH 

CHOH 

CHzOH 
i  i>  t    CHsOH 

CHOH 
2CHOH+CU  (OH) 2 

CHOH 

CHOH 

CHzOH 
i :;  >    CH2OH 

CHOH 

CHOH+3Cu(OH)2 

CHOH 

rilOH 

CH2OII 


CHtOCaOH 

CHOCuOH 

CHOCuOII+GHaO 

CHOCuOH 

CHOCuOH 

CHsOCuOH 


CeHs(OH).-,OCuO(OH)5CoHs+2  H=  O. 


CHip] 


CHO 
C 


1  Cll 


HO  ] 
}. 
CHO  J 

CHO  ] 

j^ 

CHsO  I 


Working  with  molecular  ratios  in  100  cc.  of  solution,  it  was 
found  that,  at  proportions  lower  than  1  of  mannite  to  3  of  cop- 
per sulphate,  no  precipitate  was  formed,  and  the  color  of  the 
solutions  increased  in  intensity  upon  the  addition  of  5  cc.  of 
0.5  X.  potassium  hydroxide  solution.  The  color  of  the  solution 
in  which  mannite  and  copper  sulphate  were  present  in  the  pro- 
portion of  1  to  3.5,  was  no  deeper  than  that  of  the  1  to  3  solu- 
tion, and  a  slight  precipitate  could  be  detected  in  it.  These 
facts  would  seem  to  indicate  that  the  color  in  the  case  of 
mannite  is  due  to  the  formation  of  compound  Xo.  3. 


16 


Some  experiments  were  made  to  determine  whether  nickel 
salts  as  well  as  those  of  copper  could  be  employed  for  the  de 
tection  of  mannite,  but  with  negative  results. 


Conclusions. 

(1)  The  colored  compound,  whatever  it  may  be,  which  is 
formed  when  a  little  copper  sulphate  is  added  to  an  alkaline 
solution  of  mannite,  is  decomposed  by  an  excess  (which  is  prob- 
ably a  definite  one)   of  copper  sulphate  for  every  quantity  of 
maimite.     The  alcohol  is  left  in  solution,  but  uncombined  with 
copper. 

(2)  Although  the  colored  compound  is  absorbed,  more  or 
less,  by  the  asbestos  of  the  filters,  it  can  be  removed  from  them 
by  washing  with  alkali.     In  nearly  every  case  where  colorless 
filtrates  were  obtained  while  working  with  proportions,  which 
had  in  previous  experiments  given  colored  ones,  the  alkaline 
washings  from  the  filters  were  colored. 

(3)  Alkali  of  the  strength  used  in  Fehling's  solution  can 
not  be  employed  for, the  washing  of  filters,  because  it  dissolves 
copper  hydroxide,  giving  a  blue  solution,  while  hot  water  has 
no  effect  whatever  when  used  for  washing  purposes. 

Although  mannite  cannot  be  determined  quantitatively  by 
the  method  described,  it  will  serve  very  well  for  the  detection 
of  mannite  in  the  liquid  exterior  to  the  osmotic  cell  when  leak- 
age through  the  membrane  is  suspected.  By  means  of  it  two 
milligrammes  can  easily  be  detected  in  the  presence  of 
123.92  milligrammes  of  copper  sulphate  in  100  cc.  of  liquid. 
Since  the  osmotic  pressure  of  a  0.5  N.  solution  of  mannite  is 
about  12.5  atmospheres,  a  change  of  two  milligrammes  in  its 
concentration  would  make  a  difference  of  .00028  of  an  atmos- 
phere in  the  osmotic  pressure  developed. 


17 

of  Mannitc   by  Alkaline  Solutions  of  Potassium 
Permanganate  in  the  Presence  of  Copper  Sulphate. 

The  next  question  to  come  under  consideration  in  this  con- 
nection, was  that  of  finding  some  method  for  the  quantitative 
determination  of  mannite,  and  its  oxidation  by  means  of  potas- 
sium permanganate  seemed  an  appropriate  one. 

Theoretically,  thirteen  atoms  of  oxygen  are  necessary  for  the 
complete  combustion  of  every  molecule  of  pure  mannite. 

This  was  verified,  experimentally,  as  may  be  seen  from  the 

results  given  in  the  following  tables : 

\. 

TABLE  1. 


2 

- 

e 

i 

I« 

6 

••d 

Z  C 

SI 

si 

II 

-1    s 

~. 

j£ 

X 

5 

S3 

-y»   .' 

<0 

1  ing. 

r.  <  •(  •. 

o::.27  ing. 

123.92 

mg. 

19 

hours 

at 

50° 

4.3    mg. 

12.38 

1  mg. 

occ. 

'.»::  27  mg. 

li':;.(.tL' 

mg. 

19 

hours 

at 

50 

4.4    mg. 

12.67 

1  mg. 

r,  «•<-. 

03.27  mg. 

123.92 

mg. 

19 

hours 

at 

50 

4>    mg. 

13.82 

1   mg. 

-  cc. 

03.27  mg. 

123.92 

nig. 

19 

hours 

at 

50 

4.r,    mg. 

12.96 

1  in  jr. 

.-  CC. 

o:;.2~  ing. 

123.92 

mg. 

19 

hours 

at 

50 

4.4    mg. 

12.67 

Nont' 

.-  (  •(  • 

93.27  mg. 

123.92 

mg. 

19 

hours 

at 

50 

None 

None 

i*  mg. 

r>  cc. 

93.27  mg. 

123.92 

mg. 

19 

hours 

.-it 

50 

9.2    mg. 

13.24 

2  nig. 

r.  cc. 

o:;.2~  mg. 

11':;.  '.12 

mg. 

19 

hours 

at 

50 

9.1    nig. 

13.10 

2mg. 

5cc. 

!>::.2-mg. 

123.92 

mg. 

19 

hours 

at 

50 

9.0    mg. 

12.96 

2  mg:. 

5  cc. 

93.27  mg. 

123.92 

mg. 

19 

hours 

at 

50 

8.8    mg. 

12.67 

2mg. 

5  cc. 

93.27  mg. 

123.92 

mg. 

19 

hours 

at 

50 

o.l    mg. 

13.10 

None 

5cc. 

93.27  m-. 

123.92 

mg. 

19 

hours 

at 

50 

None 

None 

3  mg. 

5cc. 

93.27  mg. 

123.92 

mg. 

19 

hours 

MI 

.-,<» 

13.31  mg. 

12.78 

3mg. 

5cc. 

93.27  mir. 

123.92 

mg. 

19 

hours 

at 

50 

13.18  mg. 

12.64 

3mg. 

5cc. 

'.•::.  27  mi:. 

123.92 

mg. 

19 

hours 

at 

50 

13.18  mg. 

12.64 

3  mg. 

5  cc. 

93^7  mg. 

123.92 

mg. 

19 

hours 

at 

50 

13.U2  mg. 

13.07 

•"•  in  jr. 

93.27  mg. 

123.92 

nig. 

10 

hours 

at 

50 

13.18  mg. 

12.64 

None 

r.  cc. 

93.27  mg. 

123.M2 

nig. 

10 

hours 

at 

.-(. 

None 

None 

4  in-. 

r,  cc. 

93.27  mg. 

12.-l.02 

mg. 

19 

hours 

at 

50 

1  7.s.",  mg. 

12.84 

4  mg. 

5cc. 

93.27  mg. 

123.92 

mg. 

19 

hours 

ar 

50 

18.16  mg. 

13.07 

4  mg. 

occ. 

93.27  mg. 

123.92 

mg. 

19 

hours 

at 

50 

17.78  mg. 

12.M 

4  mg. 

5cc. 

93.27  mg. 

123.92 

nig. 

19 

hours 

at 

50 

17.72  mg. 

12.67 

4  me. 

93.27  mg. 

123.92 

mg. 

19 

hours 

ar 

50 

20.09  mg. 

14.47 

XoiU' 

occ. 

93.27  mg. 

123.92 

ing. 

19 

hours 

at 

50 

None 

None 

~>  mg. 

93.27  mir. 

123.92 

mg. 

19 

hours 

ar 

50 

22.7omg. 

13.10 

•~  i  HIT. 

.-  <  -i  • 

93.27  me. 

12:;.!  12 

mg. 

19 

hours 

ar 

50 

22.51  nig. 

12.96 

•"  mg. 

~  ,  .,  . 

'.'::.  27  mg. 

123.H2  mg. 

19 

hours 

ar 

50 

22.rr,  mg. 

13.10 

•">  mg. 

r,  <•<-. 

'.«::.  27  mp. 

123.92 

mg. 

19 

hours 

at 

50 

22.76  mg. 

13.10 

-"•  mg. 

."i  i  •<  • 

'.»:;.L>7  mg. 

12:;.92 

mg. 

19 

hours 

ai 

50 

22.70  mg. 

13.10 

N'olH" 

~  ,  .,-. 

93.27  mg. 

12:1.02 

mg. 

10 

hours 

ar 

50 

None 

None 

18 
TABLE  2. 


c5 

"3 
s 
• 

g 

4 
O 
d 

o 

3 

il 

£ 

4 

If 

I| 

^ 

M 

t4 

y 

r*iH 

—  — 

**<o 

10  mg. 

occ. 

1  87.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

0  45.70  mg. 

13.15 

10  mg. 

Sec. 

187.05  mg. 

123.92 

mg. 

19 

hours 

nt 

50 

45.45  mg. 

13.09 

10  mg. 

5  cc. 

1  87.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

45.20  mg. 

13.02 

10  mg. 

5  cc. 

1  87.05  mg. 

123.92 

nig. 

19 

hours 

at 

50 

45.33  mg. 

13.05 

10  mg. 

5  cc. 

1  87.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

45.39  mg. 

13.07 

None 

5cc. 

1  87.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

None 

None 

20  mg. 

5  cc. 

187.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

90.28  mg. 

12.99 

20  mg. 

5  ce. 

1  87.05  mg. 

123.92 

mg. 

19 

hours 

nt 

50 

90.53  mg. 

13.04 

20  ing. 

5  co. 

1  87.05  mg. 

128.92 

mg. 

19 

hours 

at 

50 

90.07  mg. 

12.96 

20  mg. 

5cc. 

187.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

90.07  mg. 

12.96 

20  mg. 

5  cc. 

187.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

90.22  mg. 

12.99 

None 

5  cc. 

187.05  mg. 

123.92 

mg. 

19 

hours 

nt: 

no 

None 

None 

30  nig. 

5cc. 

187.05  mg. 

123.92 

nig. 

19 

hours 

at 

50 

135.1    mg. 

12.97 

30  mg. 

5cc. 

1  87.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

135.2    nig. 

12.99 

30  mg. 

5cc. 

187.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

135.1    mg. 

12.97 

30  mg. 

5  cc. 

187.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

1  35.05  mg. 

12.97 

80  mg. 

5cc. 

187.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

135.1    mg. 

12.97 

Non« 

5cc. 

187.05  mg. 

123.92 

mg. 

19 

hours 

at 

50 

None 

None 

40  mg. 

10  cc. 

361.01  mg. 

123.92 

mg. 

19 

hours 

at 

50 

1  80.95  mg. 

13.02 

40  mg. 

10  co. 

361.01  mg. 

123.92 

mg. 

19 

hours 

at 

50 

181.59ms. 

13.08 

40  mg. 

lOcc. 

361.  Olms". 

128.92 

mg. 

19 

hours 

at 

50 

182.24  mg. 

13.11 

40  mg. 

10  cc. 

361.01  mg. 

123.92 

mg. 

19 

hours 

at 

50 

181.21  mg. 

13.05 

40  mg. 

lOcc. 

361.01  mg. 

123.92 

mg. 

19 

hours 

at 

50 

181.46  mg. 

13.08 

None 

10  cc. 

301.01ms. 

123.92 

mg. 

19 

hours 

at 

no 

None 

None 

50  mg. 

lOcc. 

432       mg. 

1  23.92 

mg. 

19 

hours 

at 

50 

224.56  mg. 

12.93 

50  mg. 

10  cc. 

432       mg. 

128.92 

mg. 

19 

hours 

at 

50 

224.09  mg. 

12.90 

50  mg. 

10  oc. 

432       mg. 

123.92 

mg. 

19 

hours 

nt 

50 

224.56  mg. 

12.93 

50  mg. 

10  oc. 

432       mg. 

123.92  mg. 

19 

hours 

at 

50 

223.58  mg. 

12.89 

50  mg. 

10  cc. 

432       mg. 

123.92 

mg. 

19 

hours 

nt 

no 

223.96  mg. 

12.90 

None 

10  cc. 

432       mg. 

128.92 

mg. 

19 

hours 

nt 

no 

None 

None 

The  solutions  used  were  made  up  with  water  containing  no 
thymol. 

It  was  found  that  the  combustion  is  not  complete  until  the 
reacting  substances  have  been  allowed  to  stand  for  a  period  of 
19  hours  at  50°.  A  quantity  of  potassium  tetroxalate  equiva- 
lent to  the  permanganate  used  was  then  added,  and  the  excess 
of  tetroxalate  titrated  back  with  the  standard  permanganate 
solution ;  the  difference  between  the  two  quantities  of  perman- 
ganate added  being  the  amount  of  permanganate  reduced  dur- 
ing the'combustion. 


10 

The  mamiite  used  in  this  work  was  analyzed  by  the  electrical 
method  I'm-  I  he  combustion  of  organic  compounds,  as  devised  by 
I'rnfVssnr  Morse,  and  round  to  be  practically  pure. 

Analysis  No.  1 — Manuite  used.  .0909  gms. 

Per  cent,  hydrogen  found,  7. in;. 
Per  cent,  hydrogen  theoretical.  7.75. 
Per  cent,  carbon  theoretical,  39.54. 
Per  cent,  carbon  found,  39.47. 
Per  cent,  purity,  100.2. 

Atoms  of  oxygen  necessary  for  complete  combustion  13.03. 

Analysis  No.  L' — Maimite  used,  .0918  gins. 

Per  cent,  hydrogen  found,  7.55. 
Per  cent,  hydrogen  theoretical.  7.75. 
Per  cent,  carbon  theoretical.  oD.54. 
Per  cent,  carbon  found,  39.27. 
Percent,  purity,  99.01. 

Atoms  of  oxygen  necessary  for  complete  combustion  12.87 

This  method  can  be  used  for  the  quantitative  determination 
of  mannite  in  solutions  of  copper  sulphate.  The  reducing 
action  of  thymol  upon  alkaline  solutions  of  potassium  per- 
manganate is,  however,  considerably  greater  than  that  of  man- 
nite, which  will  probably  necessitate  the  finding  of  some  other 
means  for  coping  with  penicillium. 


PAKT  2. 

A  Determination  .of  tlie  Volumes  of  Weight-Normal  Solutions 
of  Cane  Sugar  at  15°,  20°,  25°  and  3001. 

It  is  a  well  known  fact  that  a  contraction  in  volume  takes 
place  W:lien  sugar  is  dissolved  in  water  at  ordinary  tempera- 
tures, that  is,  the  volume  of  the  solution  is  not  the  sum  of  the 
volumes  of  the  water  and  sugar  it  contains.  Determinations 
of  the  volumes  of  sugar  solutions  at  0°,  made  in  this  laboratory 
a  few  years  ago,  indicated  that  when  a  gram-molecular  weight 
of  sugar  is  dissolved  in  1000  grams  of  water  at  that  tempera- 
ture, the  volume  of  the  solution  is  about  12  cc.  less  than  the 
total  volume  of  the  water  and  sugar  composing  it. 

This  investigation  was  undertaken  for  the  purpose  of  throw- 
ing some  light  on  the  amount  of  contraction  occurring  at  15° , 
20°,  25°  and  30°  in  solutions  of  cane  sugar  of  the  concentra- 
tions thus  far  used  in  the  measurement  of  osmotic  pressure,  for 
it  is  hoped  that  a  careful  study  of  their  behavior  will  be  of 
value  in  explaining  in  a  satisfactory  manner  the  irregularities 
in  the  pressures  developed  by  them  at  lower  temperatures. 

Figure  1  represents  the  apparatus  used  in  making  the  meas- 
urements. It  consists  of  a  bulb  having  a  capacity  of  about 
100  cc.,  and  a  graduated  stem  of  an  inner  diameter  of  about  4 
mm.  To  this,  at  (c),  is  fused  a  calibrated  tube  about  400  mm. 
in  length,  having  an  interior  diameter  of  about  2  mm.  The 
exact  volume  of  the  apparatus  up  to  the  0  mark  on  the  gradu- 
ated stem,  was  determined  by  weighing  the  bulb  with  water  of 
a  known  temperature.  In  a  similar  manner  the  capacity  of  the 
stem  between  the  0  and  100  marks  was  also  determined.  The 
tube  was  calibrated  between  the  scratches  (a)  and  (b),  and 


1.  This  investigation  was  carried  out  in  collaboration  with  Mr.  F.  S1. 
Dengler,  in  whose  dissertation  the  results  obtained  for  the  even  concen- 
trations may  be  found. 


s 


100 

cc 


FlGURK    I 


22  ' 

after  it  had  been  fused  onto  the  bulb,  the  volume  of  the  space  be- 
tween the  100  mark  on  the  stem  and  the  lower  scratch  (a)  of 
the  tube  was  determined  by  means  of  a  mercury  thread. 

Eleven  such  pieces  of  apparatus  were  prepared  in  the  manner 
described,  and  weighed.  Ten  of  the  pieces  were  then  filled 
with  the  sugar  solutions  and  the  remaining  one  with  air-free 
water  to  some  point  a  little  above  the  lower  scratch  (a)  on  the 
calibrated  tube. 

A  day  or  so  after  the  apparatuses  had  been  filled  and  placed 
in  the  constant  temperature  bath,  all  of  them  were  found  to 
leak  around  the  stop-cocks  to  a  greater  or  less  extent.  They 
were  taken  down,  and  after  the  stop-cocks  had  been  carefully 
reground  with  very  fine  emory  until  they  were  tight,  the  appa- 
ratuses were  filled  again  as  before. 

The  first  measurements  were  made  at  15°,  and  in  order  to 
avoid  the  sticking  of  the  liquid  to  the  walls  of  the  tubes,  the 
solutions  and  water  were  cooled  below  this  temperature  before 
filling  the  dilatometers. 

To  secure  reliable  determinations  of  this  nature,  it  is  of  the 
utmost  importance  that  the  apparatus  be  kept  at  a  uniform 
temperature  during  the  experiments,  and  that  any  slight 
changes  in  temperature  which  may  occur  shall  be  very  gradual. 
In  order  to  secure  this  uniformity  of  temperature,  a  constant 
temperature  bath,  originally  devised  by  Morse  and  Frazer  and, 
described  as  at  present  employed  in  volume  44  of  the  American 
Chemical  Journal,  was  used  in  these  experiments. 

A  slight  change  was  necessary  in  the  construction  of  the 
bath.  The  galvanized  iron  cans  used  to  hold  the  cells  during 
the  measurement  of  osmotic  pressure  were  replaced  by  a  copper 
trough  large  enough  to  contain  all  of  the  apparatuses  at  the 
same  time.  In  a  bath  of  this  kind  temperature  fluctuations 
hardly  exceed  .01  of  a  degree. 

After  allowing  the  dilatometers  to  stand  in  the  bath  at  the 
temperature  in  question  for  a  period  of  twenty-four  hours  or 
more,  the  volumes  of  the  solutions  contained  in  them  were  read 
by  means  of  a  cathetometer.  Readings  were  then  taken  from 


day  to  day  until  the  last  three  or  four  consecutive  readings  re- 
mained constant. 

When  the  necessary  readings  had  been  made  over  the  desired 
range  of  temperature,  the  apparatuses  and  the  solutions  con- 
tained in  them  were  weighed.  From  the  weights  of  the  solu- 
tions in  the  dilatometers  and  the  measured  volumes  at  the  dif- 
ferent temperatures,  the  volumes  of  weight-normal  solutions  at 
these  temperatures  were  calculated  by  simple  proportion  in 
this  way:  Weight  of  solution  :  weight  of  the  weight-normal 
solution  : :  volume  found  :  volume  required. 

In  making  these  calculations,  a  correction  had  to  be  intro- 
duced for  the  solution  contained  in  the  hole  of  the  stop-cock. 
Its  volume  was  determined  by  means  of  mercury,  and  was  then 
added  to  the  measured  volume  of  the  solution.  The  sum  of  the 
two  volumes  is  the  actual  volume  of  the  weight  of  solution  con- 
tained in  the  apparatus  for  the  given  temperature.  Having 
thus  obtained  the  volume  of  the  weighed  amount  of  solution, 
its  specific  gravity  was  calculated.  Knowing  the  volume  of  the 
hole  in  the  stop-cock  and  the  specific  gravity  of  the  solution, 
it  was  an  easy  matter  to  determine  the  weight  of  the  solution 
contained  in  the  opening  of  the  stop-cock.  This  weight  was 
then  deducted  from  the  total  weight  of  the  solution  and  the 
value  thus  obtained  was  the  weight  of  solution  whose  volume 
had  been  measured  at  the  temperature  in  question.  This  cor- 
rected weight  was  the  one  used  for  calculating  the  actual  vol- 
umes of  the  weight-normal  solutions. 

For  the  calculations  of  the  sum  of  the  volumes  of  water  and 
sugar  contained  in  the  various  solutions,  that  is,  for  the  deter- 
mination of  the  volumes  the  solutions  should  have  provided 
there  was  no  contraction,  the  values  1.5813,  as  given  by  Ger- 
lach  and  Kopp,  and  1.5800  as  given  by  Rchroeder  for  the  specific 
gravity  of  sugar  in  a  vacuum  at  15°  were  used,  and  the  value 
.0001110  as  given  by  Joule  and  Playfair  for  the  coefficient  of 
expansion  of  sugar.  * 


24 

The  rotations  given  by  the  solutions  before  and  after  the  ex- 
periments were  as  follows: 


TABLE  1. 


Weight — Normality 
of  solutions. 
0.1 
0.3 
0.5 
0.7 
0.9 


-Rotations- 


Before. 
12.60° 
36.55° 

58.80° 
79.20° 
98.30° 


After. 
12.60 
36.55° 

08.70° 
77.50° 
75.00° 


Tables  2  and  3  contain  the  results  obtained  at  15°.  In  Table 
2,  1.5813  was  taken  as  the  specific  gravity  of  sugar,  and  1.5860 
in  table  3. 


TABLE  2  (15' 


01. 
0.3 
0.5 
0.7 
0.9 


1000.857 
1000.857 
1000.857 
1000.857 
1000.857 


!! 

21.462 

64.386 

107.310 

150.234 

193.158 


ZC  o  OS 

1022.319 
1065.243 
1108.167 
1151.091 
1194.015 


1022.417 
1063.952 
1106.576 
1147.462 
1190.359 


®Js 

§1 
II 


0.172 
1.291 
1.591 
3.629 
3.656 


TABLE  3  (15°). 


0.1 
0.3 
0.5 
0.7 
0.9 


5-2 

O  OS 

;>  ss 

1000.857 
1000.857 
1000.857 
1000.857 
1000.857 


o 
o> 

Is 

c^ 

21.394 

64.182 

106.970 

149.758 

192.546 


1022.251 
1065.039 
1107.827 
1150.615 
1193.403 


tf3 

1022.417 
1063.952 
1106.576 
1147.462 
1190.359 


fcfi 

sl 

0.104 
1.087 
1.251 
3.153 
3.044 


25 

Tables  4  and  5  contain  the  results  obtained  at  20°.  In  Table 
4.  1.5813  was  taken  as  the  specific  gravity  of  sugar  and  1.5860 
in  Table  5. 


TABLE  4    (20°) 
»  i 

•£§  c  ^  =      b 


ill 

I*: 

r   - 

"5  - 

-- 
II 

?! 

II 

11 

•^  - 

•~  z 

^"  /.    ~ 

-^  ^ 

>  y 

VI    c    ~ 

--.  - 

0.1 

1001.  7."  1 

21.474 

1023.225 

1023.111 

0.114 

0.3 

1001.751 

64.422 

1066.173 

1065.299 

0.874 

0.5 

1001.751 

1<  iT.370 

1109.121 

1107.870 

1.251 

0.7 

1001.751 

150.318 

1152.069 

1148.909 

3.160 

0.9 

1001.751 

193.266 

1105.017 

1191.827 

3.190 

TABLE 


20 


1  £§ 

'. 

S 

:       :_- 

_; 

°.s 

.  —  — 

. 

"•"    "/ 

5-    71* 

r  7 

ii!-= 

§•_• 

=  *: 

1^  ^ 

ie 

Is 

~  ?  ~f- 

~=  ~ 

•z  ^ 

=  •=- 

|| 

E^ 

0.1 

1001.751 

1'  1.406 

1023.157 

1023.111 

0.046 

0.3 

1001.751 

64.218 

1065.969 

1065.299 

0.670 

0.5 

1001.751 

107.030 

1108.781 

1107.870 

0.911 

0.7 

1001.751 

149.842 

1151.593 

1148.909 

2.684 

0.9 

1001.751 

192.654 

1194.405 

1191.827 

2.578 

Tables  6  and  7  contain  the  results  obtained  at  25.°  In  Table 
6,  1.5813  was  taken  as  the  specific  gravity  of  sugar  and  1.5860 
in  Table  7. 

TABLE  6   (25°). 


TtE- 

r  t- 

11 

'..-'- 
E^- 

s| 

|| 

—  %—    Z 

-^  s  •  — 

-*"  ^ 

-"  y 

VI   c   r: 

-<  > 

—   > 

0.1 

1002.911 

l'  1.486 

1024.397 

1024.343 

0.054 

0.3 

1002.011 

64.468 

1067.369 

1066.464 

0.905 

0.5 

1002.911 

107.430 

1110.341 

1109.404 

0.037 

0.7 

HX>2.911 

150.402 

1153.313 

1150.565 

2.748 

0.9 

1002.911 

193.374 

1195.285 

110.-J.707 

3.578 

2G 
TABLE  7   (25°). 


o 

>  ., 
.4.1  3  fee 


1*£~ 

£  •-' 

£  t^ 

C-£3 

|i 

t  £ 

^0^ 

"3  si 

3  cd 

-v-  C 

|| 

«1 

^"55  o 

>  if 

i*-  X 

X  0  * 

—  «  > 

0.1 

1002.911 

21.418 

1024.329 

1024.343(7) 

+0.044(7) 

0.3 

1002.911 

64.254 

1067.165 

1066.464 

0.701 

0.5 

1002.911 

107.090 

1110.000 

1109.404(7) 

0.596(7) 

0.7 

1002.911 

149.926 

1152.837 

1150.565 

2.272 

0.9 

1002.911 

192.762 

1195.673 

1193.707 

1.966(7) 

Instead  of  a  contraction,  an  expansion  appeared  to  have 
taken  place  in  the  case  of  the  0.1  weight-normal  solution,  which 
is  probably  due  to  some  experimental  error  not  yet  detected, 
or  possibly  to  the  fact  that  an  incorrect  value  for  the  specific 
gravity  of  sugar  has  been  taken.  The  irregularity  in  con- 
traction exhibited  by  the  0.5  weight-normal  solution  must  be 
attributed  to  experimental  error.  In  the  case  of  the  0.9  weight 
normal  solution  it  may  have  been  caused  by  decomposition  of 
the  solution  which  was  indicated  bv  the  loss  in  rotation. 


Tables  8  and  9  contain  the  results  obtained  at  30.°  In  Table 
8,  1.5813  was  taken  as  the  specific  gravity  of  sugar  and  1.5860 
in  Table  9. 


TABLE  8   (30°). 


•Sal 

lei 

gjj 

°*§ 

i| 

Ssfj 

•So^ 

[3  cs 

3SP 

S«_  e 

s~ 

g^s 

2£o 

^1 

«^  i 

^  > 

-  -3 

0.1 

1004.314 

21.497 

1025.811 

1025.777 

0.034 

0.3 

1004.314 

64.491 

1068.805 

1068.038 

0.767 

0.5 

1004.314 

107.485 

1111.799 

1111.106 

0.693 

0.7 

1004.314 

150.479 

1154.793 

1152.405 

2.388 

0.9 

1004.314 

193.473 

1197.787 

1195.631 

2.156 

TABLE  9   (30°). 

i       i  Li  ij  -If 

It                 ij  SSs  5=  5'S 

5!     £t  m  if  ^ 

0.1     1004.314     21.430  1025.744  1025.777  +0.033(7) 

0.3     1004.314     64.290  1068.604  1068.038  0.566 

0.5     1004.314  107.150  1111.464  1111.106  0.358(?) 

0.7     1004.314  150.010  1154.324  1152.405  1.919 

0.9     1004.314  192.870  1197.184  1195.631  1.553  (?) 


The  same  irregularities  appear  here  as  in  Table  7.  The  0.1 
weight-normal  solution  seemed  to  have  expanded  instead  of 
contracted.  The  0.5  weight-normal  solution  showed  a  con- 
traction, but  it  was  not  as  large  as  might  be  expected.  This  is 
also  true  for  the  0.9  weight-normal  solution.  The  various  ir- 
regularities here  may  be  attributed  to  the  same  causes  given 
under  Table  7. 

In  Tables  10,  11  and  12  are  given  the  expansion  coefficients 
of  the  various  solutions  and  of  air-free  water,  as  calculated 
from  the  experimental  data. 


TABLE  10. 


m    fi        I  i       I 

zy~  >  -  .     >«  '        ~  s-3 

o.l  100.3734  100.4680  .0947  .000189 

".:\  100.3952  100.5024  .1071  .000213 

O.o  100.5770  lOO.OOr,.;  .1176  .000234 

0.7  100.3743  100.5008  .1265  .000252 

0.9  100.4533  100.5872  .1340  .000267 
Air-free 

\vater.  100.407';  100.407H  .ossn  .000175 


The  mean  expansion  coefficient  of  air-free  water  between  1.1" 
and  20°,  as  calculated  from  the  values  given  in  Landolt-Born- 
stein,  is  .000178. 


28 
TABLE  11. 


3!!        i°g 


0.1 

100.4680 

100.5890 

.1210 

.000241 

0.3 

100.5024 

100.6323 

.1299 

.000259 

0.5 

100.6956 

100.8350 

.1394 

.000277 

0.7 

100.5008 

100.6457 

.1449 

.000288 

0.9 

100.5872 

100.7369 

.1497 

.000298 

Air-free 

water. 

100.6132 

100.6132 

.1156 

.000230 

The  mean  expansion  coefficient  of  air-free  water  between  20° 
and  25°,  as  calculated  from  the  values  given  in  Landolt-Born- 
stein,  is  .000232. 


TABLE  12. 


111 

•32 

>  Cj 

o2 

Q 

Kg 

0.1 

100.5890 

100.7298 

.1408 

.000280 

0.3 

100.6323 

100.7808 

.1485 

.000295 

0.5 

100.8350 

100.9896 

.1546 

.000307 

0.7 

100.6457 

100.8066 

.1606 

.000320 

0.9 

100.7369 

100.8983 

.1614 

.000320 

Air-free 

water 

100.6132 

100.7507 

.1375 

.000274 

The  mean  expansion  coefficient  of  air-free  water  between  25° 
and  30°,  as  calculated  from  the  values  given  in  Landolt-Born- 
stein,  is  .000280. 

In  Table  13  are  given  the  expansion  coefficients  of  the  various 
solutions  as  calculated  from  the  experimental  data  in  terms  of 
the  volumes  at  15°. 


29 
TABLE  13. 

isjj       §1^         s|  •  if« 

S^-I  fl-2  ||=  ||.-, 

0.1  .000189  .000.241  .000280 

0.3  .000213  .000259  .000296 

0.5  .000234  .000277  .000307 

0.7  .000252  .000288  .000320 

.09  .000267  .000298  .000321 

The  solutions  whose  rotation  changed  during  the  investi- 
gation all  contained  a  growth  of  some  sort,  probably  penicil- 
liuiu.  The  results  given  in  the  tables  for  the  concentrations 
greater  than  O.G  normal  are  not  reliable,  because  those  were  the 
solutions  which  contained  more  or  less  of  the  growth  men- 
tioned, and  whose  rotation  had  changed,  in  some  cases  very 
considerably. 

It  is  possible  to  correct  for  inversion  by  taking  the  loss  in 
rotation  into  account,  but  it  would  be  useless  to  do  so,  since  it 
can  not  be  stated  with  certainty  that  further  decomposition 
did  not  take  place. 

In  spite  of  the  numerous  valueless  results  obtained,  it  seems 
evident  from  the  foregoing  results;  (1)  that,  when  cane  sugar 
is  dissolved  in  water  at  any  given  temperature,  the  contraction 
in  volume  increases  with  the  concentration  of  the  solutions; 
•  -  i  that,  for  any  given  concentration,  it  decreases  with  rise  in 
temperature. 


BIOGRAPHY. 

Henry  Otto  Eyssell  was  borin  in  Kansas  City,  Mo.,  February 
23,  1885.  He  received  his  early  education  in  the  public  schools 
of  his  native  city.  In  September,  1904,  he  entered  the  Univer- 
sar  of  Missouri,  where  he  received  the  degree  of  Batchelor  of 
Arts  in  June,  1908.  In  October,  1909,  he  entered  the  Johns 
Hopkins  University  as  a  graduate  student  in  Chemistry. 


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